Hydrophobic silica powder, manufacturing method thereof and developer for electrophotography

Abstract: [Construction] A hydrophobic silica powder, treated with an amino-substituted silane compound as expressed by the following general formula (1) and organopolysiloxane, having an amount of triboelecrification relative to iron of from over +100 µC/g to up to +700 µC/g, and a hydrophobing ratio of at least 60% as measured by the transmittance method: General formula (1): R¹SiR² 3-n R³ n where, R¹ is an amino-substituted alkyl group having a carbon number of from 1 to 10; R² is an alkyl group having a carbon number of from 1 to 5; R³ is Cl, Br or an alkoxy group having a carbon number of from 1 to 5; and n is an integer of from 1 to 3. The treatment should preferably be applied with silica powder in the suspended state. [Effects] When adding the silica powder as an agent for improving fluidity to a toner, there is available a developer for electrophotography having a stable electrification and excellent in fluidity, and it is possible to clearly develop an electrostatic image free from fog and obtain stable developing properties with a long service life.

Description: [FIELD OF THE INVENTION] The present invention relates to a hydrophobic silica powder useful as a toner additive, a manufacturing method thereof and a developer for electrophotography which contains same. [PRIOR ART DESCRIPTION] A powder known as hydrophobic silica powder (hereinafter simply referred to as "hydrophobic silica") made by hydrophobing a fine silica (SiO 2 ) powder surface with an organic substance is widely used as a fluidity improving agent of toner in the area of electrophotography including copying machines, laser printers and facsimile machines for ordinary paper. In these cases, triboelectrification relative to a carrier such as iron or iron oxide is one of the important properties. Depending upon electric charge of the photosensitive material used for the formation of an electrostatic image, a toner of the counter polarity thereof is employed. To avoid hindering electrification property of the toner or causing a serious change thereof, therefore, it is desirable to use a hydrophobic silica of the same polarity as that of toner and that the electrification should be stable. Since a chalcogen material such as selenium conventionally used as a popular photosensitive material has the positive polarity, a toner negatively electrified has been used for development, and consequently, a hydrophobic silica of the negative electrification type has been employed. Photosensitive materials comprising organic semiconductors developed recently are of the negative polarity type, so that positively electrified toners are employed, and there is a demand for a hydrophobic silica having a large amount of positive electrification. The amount of triboelectrification of a hydrophobic silica relative to iron presents a positive or negative value depending upon the kind of the particular organic treatment agent used for hydrophobing treatment. As a method for obtaining a silica exhibiting positive electrification, there is known a method of treating the silica powder surface with an amino-substituted silane compound (Japanese Laid-Open Patent Publication No. 53-22,447). This silica powder treated with the amino-substituted silane compound, being hydrophilic as it is, ones doubly treated with hexamethyldisilazane are usually used to convert it hydrophobic. However, even by doubly treating with the amino-substituted silane and hexamethyldisilazane, hydrophobicity of the silica powder is still insufficient, and problems such as susceptibility to environment, particularly humidity, uncertain amount of electrification, and a short service life of the developer have been pointed out. Another problem has been the insufficient amount of electrification. [PROBLEMS TO BE SOLVED] An object of the present invention is to provide a hydrophobic silica powder having both a sufficient hydrophobicity and a high positive triboelectrification relative to iron, and a manufacturing method thereof. Another object of the present invention is to provide a developer for electrophotography excellent in fluidity, having a stable electrification property, by adding the above-mentioned silica powder to the toner. [MEANS TO SOLVE PROBLEMS] As a result of extensive studies, the present inventors found that the above-mentioned object were achieved by surface treatment of a silica powder used in combination with amino-substituted silane compound and organopolysiloxane. In summary, the present invention provides a hydrophobic silica powder as claimed in claim 1. According to the present invention, there is also provided a method of manufacturing the above-mentioned hydrophobic silica powder as claimed in claim 4, which comprises the step of bringing suspended silica powder into contact with the amino-substituted silane compound and organopolysiloxane, and an electrophotographic developer as claimed in claim 9. The treatment agents used for the treatment of the silica powder in the present invention are amino-substituted silane compound expressed by the above-mentioned general formula (1) and organopolysiloxane. The amino-substituted silane compound can impart positive electrification to the silica powder through reaction with the silica surface. The following compounds are typical examples, but ones other than these examples may be used as well: H 2 N(CH 2 ) 3 Si(OEt) 3 H 2 N(CH 2 ) 2 NH(CH 2 ) 3 Si(OMe) 3 H 2 N(CH 2 ) 2 NH(CH 2 ) 3 SiMe(OMe) 2 C 6 H 5 NH(CH 2 ) 3 Si(OMe) 3 H 2 N(CH 2 ) 2 NH(CH 2 ) 3 SiCl 3 Organopolysiloxane is known also as silicone, and has been applied as a water repellent. There is no particular restriction on organopolysiloxane used in the present invention so far as a sufficient hydrophobicity can be imparted to the silica surface, but preferable ones in practice include those having methyl radical, phenyl radical or hydro radical as the subsituent. More specifically, dimethylpolysiloxane, diphenylpolysiloxane and methylhydropolysiloxane are typical examples. In the aspect of treatment operation, viscosity should preferably be within a range of from 10 to 1,000 cs, but one with a higher viscosity may well be applicable by diluting with an appropriate solvent. The particularly preferable organopolysiloxane is dimethylpolysiloxane which is a low-viscosity liquid. Typical commercially available organopolysiloxane products suitable for use in the present invention include KF-96, KF-99 and KF-56 manufactured by Shin-Etsu Silicone Co., Ltd. and SH 200, SH 510 and SH 1107 manufactured by Toray Dow-Corning Co., Ltd. The silica powder used in the present invention consists of fine particles known as colloidal silica. No particular restriction is imposed on the particle size of silica so far as the electrification property thereof is suitable to a particular application required. The particle size should however preferably be at least 50 m 2 /g in general in terms of specific surface area. The optimum average primary particle size of silica powder is within a range of from about several nm to several hundred nm. The hydrophobic silica powder of the present invention has an amount of triboelectrification relative to iron of from + 200 µC/g to up to +700 µC/g, and a hydrophobing ratio of at least 60% as measured by the transmittance method, as a result of treatment with an amino-substituted silane compound and organopolysiloxane. Measurement of the amount of triboelectrification relative to iron may be accomplished in accordance with any of the methods already disclosed in literature (for example, Shikizai [Coloring Materials], 55[9], 630-636, 1982). An amount of triboelectrification of up to +100 µC/g may reduce the positive electrification of the toner itself, and an amount of over +700 µC/g, on the other hand, may lead to an adverse effect of an unstable electrification of the toner. In practice, the amount of triboelectrification relative to iron is within a range of from +200 to +500 µC/g. The transmittance method is for experimentally determining the hydrophobing ratio of treated silica powder, in which the measurement is accomplished in the following procedure. The treated silica powder in an amount of 1.0 g and 100 ml water are put in an extracting flask, and intensely shaked and stirred for five minutes. Then, the flask is held stationary for one minute, and a slight amount of suspension is extracted from the bottom of the flask. The transmittance of 550 nm beam through this liquid, as expressed with the transmittance of pure water as 100%, is adopted as the hydrophobing ratio of that silica powder. According as the value of hydrophobing ratio thus measured is higher, hygroscopicity of the silica powder decreases, with smaller change in the amount of electrification of toner relative to humidity, and the effect of preventing aggregation is improved, thus bringing about a high value of utilization. In practice, a hydrophobing ratio of at least 60% suffices. A hydrophobing ratio of at least 70% is particularly preferable. The hydrophobic silica powder of the present invention is manufactured by surface-treating a silica powder of an appropriate particle size (or specific surface area) with at least a kind of amino-substituted silane compound and at least a kind of organopolysiloxane. This surface treatment may be accomplished by any of the various known methods. A preferable method for obtaining a uniformly treated hydrophobic silica without aggregation comprises rendering the silica powder into a suspended state to bring this powder into contact with the above-mentioned treatment agents. Silica powder, comprising very fine particles, can be brought into a suspended state through mechanical stirring alone. The treatment can therefore be accomplished by subjecting the silica powder to sufficient mechanical stirring into a suspended state, and adding an amino-substituted silane compound and organopolysiloxane, diluted with a solvent as required, simultaneously or sequentially (in any order) by dripping or spraying. As a result of this treatment, the silica powder surface begins to show a sufficient positive amount of triboelectrification on a level of over +100 µC/g relative to iron through reaction with the amino-substituted silane compound (between the hydroxyl group of silica and alkoxy group or halogen group of the amino-substituted silane compound). At the same time, the silica powder surface is hydrophobed by covering the surface with organopolysiloxane. Any of such appropriate solvents as alcohol, ketone and hydrocarbons may be used as the diluent in response to the viscosity of the amino-substituted silane compound and organopolysiloxane actually employed. As a catalyst for increasing reactivity of the amino-substituted silane compound, it is desirable to use an organic amine such as diethyleneamine simultaneously with the amino-substituted silane compound, or to blow ammonia gas into the silica powder to be treated. After addition of the treatment agent, the reaction is completed by heating at a temperature within a range of from 100 to 250ºC in nitrogen atmosphere to eliminate the solvent (when used). Depending upon the heating temperature, the heating time should usually be within a range of from one to five hours including the temperature raising time. The above-mentioned treatment should preferably be carried out in an atmosphere of nitrogen or other inert gas to prevent oxidation of the treatment agent. The consumption of the above-mentioned two treatment agents necessary for obtaining the hydrophobic silica of the present invention resulting from the above-mentioned treatment, i.e., the silica powder having an amount of triboelectrification relative to iron of from + 200 µC/g to up to +700 µC/g and a hydrophobing ratio of at least 60% as measured by the transmittance method varies with conditions such as the specific surface area of the silica powder to be treated and the kinds of the treatment agents. The necesssary consumption of the treatment agents can be easily determined through an experiment. In the case of a silica powder having a specific surface area of 130 m 2 /g, for example, a silica powder provided with the above-mentioned properties is available by limiting the consumption of amino-substituted silane compound relative to the weight of silica to be treated within a range of from 3.0 to 15.0 wt.%, or more preferably, of from 4.0 to 10.0 wt.%, and that of organopolysiloxane within a range of from 3.0 to 15.0 wt.%, or more preferably, of from 3.0 to 10.0 wt.%. While the utilization ratio of the two treatment agents is not limited so far as a hydrophobic silica having the above-mentioned properties are available through the treatment, the weight ratio of amino-substituted silane compound to organopolysiloxane should usually be within a range of from 10:3 to 3:10. The hydrophobic silica of the present invention treated with amino-substituted silane compound and organopolysiloxane as described above may be added to the toner by an usual method. The toner generally contains a pigment and an electric charge control agent in slight amounts, in addition to a thermoplastic resin. The developer for electrophotography of the present invention is available by mixing this toner with a carrier (usually an iron powder or an iron oxide powder) and other additive. This developer may, so far as the toner contains the hydrophobic silica of the present invention blended therein, have the other constituents in the same manner as in the conventional one, and the composition may be any of unitary and binary composition systems. Even when the hydrophobic silica powder of the present invention is contained in a relatively large quantity in the toner, properties of the toner are never impaired, and it is possible to sufficiently improve fluidity of the toner. It was furthermore confirmed that the resultant developer became harder to be affected by humidity or temperature and occurrence of fog or quality degradation of image became more difficult. The amount of the hydrophobic silica of the present invention added to toner may be an amount which permits improvement of the above-mentioned properties under the effect of the resultant developer, with no particular restrictions, but should usually be within a range of from 0.05 to 5.0 wt.% relative to the total weight of toner. [EXAMPLES] For the purpose of assisting understanding of the present invention, the following paragraphs present some examples and comparative examples which should not however be interpreted to limit in any manner the present invention. In the examples, measurement of hydrophobing ratio by the transmittance method was carried out by the above-mentioned procedure, and measurement of the amount of triboelectrification was accomplished in accordance with a method disclosed in the "Shikizai (Coloring Materials)," 55[9], 630-636, 1982. EXAMPLE 1 A heated and dried silica powder (specific surface area: 130 m 2 /g) in an amount of 20 g was placed in a stainless steel tube, and a treatment solution having the following composition was sprayed at the room temperature while mechanically stirring so as to cause suspension of silica particles in nitrogen atmosphere. Composition of the treatment agent: Amino-substituted silane compound [H 2 N(CH 2 ) 3 Si(OEt) 3 ] 1.00 g Dimethylpolysiloxane [made by Shin-Etsu Kagaku Co.; KF-96, 50 cs] 1.00 g Diethylamine a few drops n-propanol 5.0 ml After spraying followed by further stirring at the room temperature for 30 minutes, external heating was carried out under a nitrogen gas flow. External heating was accomplished by raising temperature to 150ºC for 40 minutes, then holding the silica powder at this temperature for 30 minutes, and then leaving same to cool to the room temperature. The thus treated silica powder had a hydrophobing ratio of 72% and an amount of triboelectrification relative to iron of +467 µC/g. As a result of treatment of the silica powder in the suspended state, the silica powder after treatment showed no sign of aggregation and a uniform treatment was ensured. A toner was prepared by dispersing, in a styrene-acrylic acid copolymerized resin, 18 wt.% carbon (pigment) and 3 wt.% nigrosine (electric charge control agent) relative to the amount of the resin, crushing the dispersed mixture, and mixing 1 g silica powder mentioned above into a colored resin powder in an amount of 100 g resulting from classification into 10 to 20 µm. Furthermore, 30 g this toner were mixed with 1,000 g iron oxide powder to form a developer for electrography. This developer had an amount of triboelectrification of +16 µC/g. A service life test was conducted by charging this developer into a copying machine: no fog was produced in the image even after copying more than about 24,000 sheets. Moreover, it gave a satisfactory image even in an environment comprising a high temperature and a high humidity (28ºC and 85%RH). A developer prepared by adding no silica powder showed an amount of triboelectrification of +15 µC/g. Blending of the hydrophobic silica powder of the present invention therefore prevented occurrence of any serious change in the triboelectrification of the toner. A developer not containing this silica powder led to a poor fluidity of toner, resulting in clogging at the toner feeding section. EXAMPLE 2 A heated and dried silica powder (specific surface area: 130 m 2 /g) in an amount of 20 g was placed in a stainless steel container, and a treatment solution of the following composition was dripped at the room temperature while mechanically stirring so as to cause suspension of silica particles in nitrogen atmosphere. Composition of treatment agent: Amino-substituted silane compound [H 2 N(CH 2 ) 3 Si(OEt) 3 ] 0.60 g Dimethylpolysiloxane [made by Shin-Etsu Kagaku Co.; KF-96, 50 cs] 1.50 g Diethylamine a few drops n-propanol 5.0 ml After the completion of dripping, stirring at the room temperature and external heating were carried out in the same manner as in the Example 1. The silica powder after treatment had a hydrophobing ratio of 86% and an amount of triboelectrification relative to iron of +251 µC/g. Since the consumption of the amino-substituted silane compound was smaller and the consumption of dimethylpolysiloxane was larger as compared with those in the Example 1, the amount of triboelectrification was smaller and hydrophobicity was higher. Then, a toner was prepared with the use of silica powder in the same manner as in the Example 1, and a developer was prepared with the use of this toner in the same manner as in the Example 1. This developer had an amount of triboelectrification of +16 µC/g. A service life test was carried out by placing the developer into a commercially available copying machine: no fog occurred in the copied image even after copying more than 22,000 sheets. A satisfactory image was achieved even in an environment comprising a high temperature and a high humidity (28ºC and 85%RH). A developer prepared without addition of silica powder had an amount of triboelectrification of +16 µC/g. EXAMPLE 3 A silica powder was treated, and a toner and a developer for electrophotography were prepared in the same manner as in the Example 1, except that the composition of the treatment agent was altered as follows: Amino-substituted silane compound [H 2 N(CH 2 ) 3 Si(OEt) 3 ] 1.00 g Dimethylpolysiloxane [made by Shin-Etsu Kagaku Co.; KF-96, 50 cs] 2.00 g Diethylamine a few drops n-propanol 5.0 ml After the treatment, the silica powder had a hydrophobing ratio of 82% and an amount of triboelectrification relative to iron of +570 µC/g. The resultant developer had an amount of triboelectrification of +17 µC/g. A service life test was carried out by charging this developer into a commercially available copying machine: no fog was produced in the copied image even after copying more than 25,000 sheets. Furthermore, a satisfactory image was obtained even in an environment comprising a high temperature and a high humidity (28ºC and 85%RH). A developer prepared without addition of silica powder had an amount of triboelectrification of +16 µC/g. EXAMPLE 4 A silica powder was treated, and a toner and a developer for electrophotography were prepared in the same manner as in the Example 1, except that the composition of the treatment agent was altered as follows: Amino-substituted silane compound [H 2 N(CH 2 ) 3 Si(OEt) 3 ] 1.50 g Dimethylpolysiloxane [made by Sin-Etsu Kagaku Co.; KF-96, 50 cs] 2.00 g Diethylamine a few drops n-propanol 5.0 ml After the treatment, the silica powder had a hydrophobing ratio of 81%, and an amount of triboelectrification relative to iron of +682 µC/g. The resultant developer had an amount of triboelectrification of +17 µC/g. A service life test was carried out by charging this developer into a commercially available copying machine: no fog was produced in the copied image even after copying more than 26,000 sheets. Furthermore, a satisfactory image was obtained even in an environment comprising a high temperature and a high humidity (28ºC and 85%RH). A developer prepared without addition of silica powder had an amount of triboelectrification of +16 µC/g. EXAMPLE 5 A silica powder was treated, and a toner and a developer for electrophotography were prepared in the same manner as in the Example 1, except that the composition of the treatment agent was altered as follows: Amino-substituted silane compound [H 2 N(CH 2 ) 2 NH(CH 2 ) 3 SI(OMe) 3 ] 1.00 g Dimethylpolysiloxane [made by Shin-Etsu Kagaku Co.; KF-96, 50 cs] 1.00 g Diethylamine a few drops Acetone 5.0 ml After the treatment, the silica powder had a hydrophobing ratio of 84%, and an amount of riboelectrification relative to iron of +538 µC/g. The resultant developer had an amount of triboelectrification of +16 µC/g. A service life test was carried out by charging this developer into a commercially available copying machine: no fog was produced in the copied image even after copying more than 23,000 sheets. Furthermore, a satisfactory image was obtained even in an environment comprising a high temperature and a high humidity (28ºC and 85%RH). A developer prepared without addition of silica powder had an amount of triboelectrifiction of +16 µC/g. EXAMPLE 6 A heated and dried silica powder (specific surface area: 130 m 2 /g) in an amount of 20 g was placed in a stainless steel container, and a treatment solution of the following composition was sprayed at the room temperature while mechanically stirring so as to cause suspension of silica particles in nitrogen atmosphere. Composition of treatment solution: Amino-substituted silane compound [H 2 N(CH 2 ) 2 NH(CH 2 ) 3 SiCl 3 ] 1.00 g Dimethylpolysiloxane [made by Shin-Etsu Kagaku Co.; KF-96, 50 cs] 1.00 g n-hexane 5.0 ml After the completion of spraying, followed by stirring at the room temperature for 30 minutes, ammonia gas was blown for five minutes, and the external heating was conducted under a nitrogen gas flow. External heating was accomplished by raising temperature to 180ºC in 40 minutes, and holding same at this temperature for 30 minutes. The silica powder was then left to cool to the room temperature. The treated silica powder had a hydrophobing ratio of 79%, and an amount of triboelectrification relative to iron of +553 µC/g. Then, a toneer was prepared using this silica powder in the same manner as in the Example 1, and a developer was prepared using this toner in the same maner as in the Example 1. This developer had an amount of triboelectrification of +16 µC/g. A service life test was carried out by placing the developer into a commercially available copying machine: no fog occurred in the copied image even after copying more than 23,000 sheets. A satisfactory image was achieved even in an environment comprising a high temperature and a high humidity (28ºC and 85%RH). A developer prepared without adding silica powder had an amount of triboelectrification of +15 µC/g. EXAMPLE 7 A heated and dried silca powder (specific surface area: 130 m 2 /g) in an amount of 20 g was placed in a stainless steel container, and a treatment solution of the following composition was sprayed at the room temperature while mechanically stirring so as to cause suspension of silica particls in nitrogen atmosphere. Composition of treatment agent: Amino-substituted silane compound [H 2 N(CH 2 ) 3 Si(OEt) 3 ] 1.00 g Methylhydropolysiloxane [made by Shin-Etsu Kagaku Co.; KF-99, 50 cs] 1.00 g Methylamine a few drops n-propanol 5.0 ml After the completion of spraying, followed by stirring at the room temperature for 30 minutes, external heating was applied under a nitrogen gas flow. External heating was accomplished by raising temperature to 170ºC in 40 minutes, and holding same at this temperature for 30 minutes. The silica powder was then left to cool to the room temperature. The treated silica powder had a hydrophobing ratio of 88%, and an amont of triboelectrification relative to iron of +513 µC/g. Then, a toner was prepared using this silica powder in the same manner as in the Example 1, and a developer was prepared using this toner in the same manner as in the Example 1. This developer had an amount of triboelectrification of +17 µC/g. A service life test was carried out by placing the developer into a commercially available copying machine: no fog occurred in the copied image even after copying more than 25,000 sheets. A satisfctory image was achieved even in an environment comprising a high temperature and a high humidity (28ºC and 85%RH). A developer prepared without adding silca powder had an amount of triboelectrification of +16 µC/g. COMPARATIVE EXAMPLE 1 A silica powder was treated, and a toner and a developer for electrophotography were prepared in the same manner as in the Example 1, except that the composition of the treatment agent was altered as follows: Amino-substituted silane compound [H 2 N(CH 2 ) 3 Si(OEt) 3 ] 1.00 g Diethylamine a few drops n-propanol 5.0 ml After the completion of treatment, the silica powder had a hydrophobing ratio of 18%, and an amount of triboelectrification relative to iron of +285 µC/g. The resultant developer had an amount of triboelectrification of +16 µC/g. Because the treatment agent did not contain organopolysiloxane, the silica powder after treatment showed a very low hydrophobicity. A service life test was carried out by charging this developer into a commercially available copying machine: fog occurred in the copied image upon copying about 5,000 sheets. Fog occurred in the copied image upon copying about 1,500 sheets in an environment comprising a high temperature and a high humidity (28ºC and 85%RH). A developer prepared without adding silica powder had an amount of triboelectrification of +15 µC/g. COMPARATIVE EXAMPLE 2 A silica powder was treated, and a toner and a developer for electrophotography were prepared in the same manner as in the Example 1, except that the composition of the treatment agent was altered as follows: Amino-substituted silane compound [H 2 N(CH 2 ) 3 Si(OEt) 3 ] 1.00 g Hexamethyldisilazane (HMDS) 1.00 g Diethylamine a few drops n-propanol 5.0 ml After the treatment, the silica powder had a hydrophobing ratio of 24%, and an amount of triboelectrification relative to iron of +187 µC/g. The resultant developer had an amaount of triboelectrification of +18 µC/g. When organopolysiloxane was replaced by HMDS in accordance with the prior art, the amount of triboelectrification decreased and hydrophobicity was insufficient. A service life test was carried out by charging this developer into a commercially available copying machine: fog occurred in the copied image upon copying about 7,000 sheets. Fog occurred in the copied image upon copying about 5,500 sheets in an environment comprising a high temperature and a high humidity (28ºC and 85%RH). A developer prepared without adding silica powder had an amount of triboelectrification of +16 µC/g. [EFFECTS OF THE INVENTION] As is clear from the above description, the treament of a silica powder by the simultaneous use of an amino-substituted silane compound and organopolysiloxane makes it available a silica powder having an amount of triboelectrification relative to iron of from + 200 µC/g to up to +700 µC/g, and a hydrophobing ratio of at least 60% as measured by the transmittance method. When the treatment is applied with the silica powder in the suspended state, it is possible to obtain a hydrophobic silica uniformly treated without aggregation. If this silica powder is added as an agent for improving fluidity to a toner for electrophotography, it is possible to clearly develop an electrostatic image free from fog, and obtain stable developing properties with a long service life.

Claims: Hydrophobic silica powder obtainable by treating silica powder with an amino-substituted silane compound as expressed by the following general formula (1): R 1 SiR 2 3-n R 3 n wherein R 1 is an amino-substituted alkyl group having a carbon number of from 1 to 10; R 2 is an alkyl group having a carbon number of from 1 to 5; R 3 is Cl, Br or an alkoxy group having a carbon number of from 1 to 5; and n is an integer of from 1 to 3; and an organopolysiloxane, said hydrophobic silica powder having an amount of triboelectrification relative to iron of from +200 µC/g to up to +700 µC/g and a hydrophobing ratio of at least 60% as measured by the transmittance method, said transmittance method being accomplished by: putting an amount of 1,0 g of the treated silica powder and 100 ml water in an extracting flask; intensely shaking and stirring the flask for five minutes; holding the flask stationary for one minute; extracting a slight amount of suspension from the bottom of the flask; measuring the transmittance of 550 nm beam through this liquid; and adopting it as the hydrophobing ratio of that silica powder, as expressed with the transmittance of pure water as 100%, with the proviso that the organopolysiloxane used for treating the silica powder has no N in the side chain. Hydrophobic silica powder according to Claim 1, wherein the hydrophobic silica powder has a hydrophobing ratio of at least 70%. Hydrophobic silica powder according to any of Claims 1 to 2, wherein the amino-substituted silane compound is selected from the group consisting of: H 2 N(CH 2 ) 3 Si(OEt) 3 , H 2 N(CH 2 ) 2 NH(CH 2 ) 3 Si(OMe) 3 , H 2 N(CH 2 ) 2 NH(CH 2 ) 3 SiMe(OMe) 2 , C 6 H 5 NH(CH 2 ) 3 Si(OMe) 3 , and H 2 N(CH 2 ) 2 NH(CH 2 ) 3 SiCl 3 . Method of manufacturing a hydrophobic silica powder as claimed in Claims 1 to 3, which method comprises the step of bringing suspended silica powder into contact with said amino-substituted silane compound and said organopolysiloxane. Method of manufacturing a hydrophobic silica powder according to Claim 4 wherein a catalyst for increasing the reactivity of the amino-substituted silan compound is used. Method of manufacturing a hydrophobic silica powder according to Claim 5, wherein the catalyst is an organic amine or ammonia gas. Method of manufacturing a hydrophobic silica powder according to Claim 6, wherein the amine is diethyleneamine or methylamine. Method of manufacturing a hydrophobic silica powder according to Claim 5, wherein the catalyst is added to the amino-substituted silane compound and the organopolysiloxane simultaneously or in sequence. Electrophotographic developer consisting of a toner and the hydrophobic silica powder as claimed in any of Claims 1 to 3.

Inventors: ARAKAWA SHIGEHIRO, NAKAMURA AKIHIRO, NISHIHARA AKIRA, ARAKAWA, SHIGEHIRO, NAKAMURA, AKIHIRO, NISHIHARA, AKIRA, ARAKAWA, SHIGEHIRO, C/O CHUO-KENKYUSHO, NAKAMURA, AKIHIRO, C/O CHUO-KENKYUSHO, NISHIHARA, AKIRA, C/O CHUO-KENKYUSHO
Applicants: MITSUBISHI MATERIALS CORP, MITSUBISHI MATERIALS CORPORATION
Application year: 1994
Main classification: G03G9
IPC codes: C09C1, G03G9, C01B33